The quest for complexes with a coordinative gold-bismuth bond

Article abstract of DOI:10.1021/om030464g

In attempts to prepare gold(I) bismuthine compounds of the type R₃Bi-AuX with a coordinative Au-Bi bond, the complexes (C₄H₈S)AuCl, (Me₂S)AuCl, (C₄H₈S)AuC₆F₅, (Ph₃P)-AuCl, and [(Ph₃P)Au]BF₄ were reacted with the tertiary bismuthines Me₃Bi, MePh₂Bi, Ph₃Bi, (2-MeO-C₆H₄)₃Bi, and (2-Me₂NCH₂-C₆H₄)₃Bi in different molar ratios in dichloromethane at low temperatures. In all reactions the bismuthines acted as alkylating or arylating agents for gold to give organogold complexes. The products with the sulfur ligands were generally unstable and decomposed above -50°C. With phosphine ligands, the organogold(I) complexes can be traced in the reaction mixtures by NMR spectroscopy. The primary product (Ph₃P)-AuPh is aurated further by [(Ph₃P)Au]BF₄ to give C₆H₅[Au(PPh₃)]₂BF₄. A stable dinuclear arylgold complex was obtained in the reactions of the thioether complexes with tris(2-((dimethylamino)methyl)phenyl)bismuthine, and the structure of this 10-membered metallacyclic compound has been determined: [-Au-C₆H₄CH₂NMe₂-]₂. The molecules feature strong transannular aurophilic interactions. The crystal structure of tris(2-methoxyphenyl)-bismuthine has also been determined.

Full text of DOI:10.1021/om030464g

Organometallics 2003, 22, 4079-4083
4079
Th e Qu est for Com p lexes w ith a Coor d in a tive
Gold -Bism u th Bon d
Oliver Schuster, Annette Schier, and Hubert Schmidbaur*
Anorganisch-chemisches Institut der Technischen Universita¨t Mu¨nchen, Lichtenbergstrasse 4,
85747 Garching, Germany
Received J une 17, 2003
In attempts to prepare gold(I) bismuthine compounds of the type R3Bi-AuX with a
coordinative Au-Bi bond, the complexes (C4H8S)AuCl, (Me2S)AuCl, (C4H8S)AuC6F5, (Ph3P)-
AuCl, and [(Ph3P)Au]BF4 were reacted with the tertiary bismuthines Me3Bi, MePh2Bi, Ph3-
Bi, (2-MeO-C6H4)3Bi, and (2-Me2NCH2-C6H4)3Bi in different molar ratios in dichloromethane
at low temperatures. In all reactions the bismuthines acted as alkylating or arylating agents
for gold to give organogold complexes. The products with the sulfur ligands were generally
unstable and decomposed above -50 °C. With phosphine ligands, the organogold(I) complexes
can be traced in the reaction mixtures by NMR spectroscopy. The primary product (Ph3P)-
AuPh is aurated further by [(Ph3P)Au]BF4 to give C6H5[Au(PPh3)]2BF4. A stable dinuclear
arylgold complex was obtained in the reactions of the thioether complexes with tris(2-
((dimethylamino)methyl)phenyl)bismuthine, and the structure of this 10-membered metal-
lacyclic compound has been determined: [-Au-C6H4CH2NMe2-]2. The molecules feature
strong transannular aurophilic interactions. The crystal structure of tris(2-methoxyphenyl)-
bismuthine has also been determined.
ally a paucity of data on gold-bismuth compounds other
than binary or polynary alloys.12
In tr od u ction
In the present study we have therefore probed a series
of seemingly straightforward synthetic pathways which
could lead to gold(I) bismuthine complexes. It was
expected that compounds with an Au-Bi donor/acceptor
bond should exhibit properties very different from those
of the N, P, As, and Sb analogues, owing (a) to the
unique character of the bismuth atom as the most
electropositive group V element, (b) to the large atomic
radius of the heaviest stable element in the periodic
table, and (c) to strong relativistic effects.
Our attempts to prepare a complex of the type (R3-
Bi)AuX were not successful. All pertinent reactions took
a different course, but from the nature of the products
the true reactivity pattern could be elucidated. It turned
out that tertiary bismuthines are powerful alkylating
or arylating agents for gold(I). Any bismuthine complex
intermediate which may be generated will immediately
be subject to heterolytic Bi-C cleavage and Au-C bond
formation with concomitant Au-Bi separation. Tertiary
bismuthines R3Bi thus are genuine organometallic
reagents comparable in their mode of reactivity to
Grignard, organolithium, or organozinc compounds,
which are all known to alkylate or arylate gold(I)
complexes.7
Tertiary phosphines, R3P, are the most widely em-
ployed ligands in late-transition-metal chemistry.1 In
contrast, the coordination chemistry with tertiary ar-
sines, R3As, and stibines R3Sb is much less developed,2
even though the introduction of these ligands may have
certain advantages, regarding in particular the stereo-
chemistry and the trans influence or trans effect in their
complexes.3 Finally, tertiary bismuthines R3Bi were only
rarely used as donor components in any donor/acceptor
complexes,2 and less than half a dozen coordination
compounds have been fully characterized.4-6
In the course of extensive studies in the molecular
and supramolecular chemistry of gold(I) complexes, we
have investigated a large number of prototypes with
tertiary amines, phosphines, and arsines mainly of the
general formula (R3E)AuX with E ) N, P, As and X )
(pseudo)halide, alkoxide, siloxide, mercaptide, etc.7,8
A
literature survey has shown that the number of related
compounds with tertiary stibines is very small in-
deed2,9-11 and that no gold(I) complex with a tertiary
bismuthine ligandsfeaturing a discrete Au-Bi donor/
acceptor bondshas ever been reported. There is gener-
* Corresponding author.
(7) Gold, Progress in Chemistry, Biochemistry and Technology;
Schmidbaur, H., Ed.; Wiley: Chichester, U.K., 1999.
(8) Schneider, D.; Nogai, S.; Schier, A.; Schmidbaur, H. Inorg. Chim.
Acta 2003, 352, 179.
(9) Uso´n, R.; Laguna, A.; Vicente, J .; Garcia, J .; J ones, P. G.;
Sheldrick, G. M. J . Chem. Soc., Dalton Trans. 1981, 655.
(10) J ones, P. G. Acta Crystallogr., Sect. C: Cryst. Struct. Commun.
1992, 48, 1487.
(11) Arcas, A.; Lautner, J .; Vicente, J .; J ones, P. G. J . Chem. Soc.,
Dalton Trans. 1190, 451.
(12) Gmelin Handbook of Inorganic Chemistry; Springer: Berlin,
1995; Gold, Suppl. Vol. B3.
(1) Wilkinson, G.; McCleverty, J . A. Comprehensive Coordination
Chemistry; Pergamon: Oxford, U.K., 1987.
(2) Champness, N. R.; Levason, W. Coord. Chem. Rev. 1994, 133,
115.
(3) Pechmann, T.; Brandt, C. D.; Werner, H. J . Chem. Soc., Dalton
Trans. 2003, 1495 and references therein.
(4) Holmes, N. J .; Levason, W.; Webster, M. J . Organomet. Chem.
1997, 545-546, 111.
(5) Carty, A. J .; Taylor, N. J . J . Chem. Soc., Chem. Commun. 1979,
639.
(6) Schumann, H.; Eguren, L. J . Organomet. Chem. 1991, 403, 183.
10.1021/om030464g CCC: $25.00 © 2003 American Chemical Society
Publication on Web 08/27/2003

4080 Organometallics, Vol. 22, No. 20, 2003
Schuster et al.
Sch em e 2
Resu lts a n d Discu ssion
Syn th esis. The most common standard reagents for
the preparation of gold(I) complexes of the type L-Au-X
were used, including (tetrahydrothiophene)gold chloride,
(tht)AuCl, (dimethyl sulfide)gold chloride, (Me2S)AuCl,
pentafluorophenyl(tetrahydrothiophene)gold, (tht)AuC6F5,
(triphenylphosphine)gold chloride, (Ph3P)AuCl, and
(triphenylphosphine)gold tetrafluoroborate, (Ph3P)Au+-
BF4-. The bismuth components were trimethyl-, diphen-
ylmethyl-, triphenyl-, tris(2-methoxyphenyl)- and tris-
(2-((dimethylamino)methyl)phenyl)bismuthine. The re-
actions were generally carried out under very mild
conditions (-78 to -50 °C, inert gas blanket, protection
against light) to minimize thermal and photochemical
decomposition. The bismuthines were used in stoichio-
metric quantities (1:1) or in large excess (e.g. 1:4). Even
so, most experiments led to extensive decomposition, as
noted from the formation of deep purple colloids in
solution followed by the appearance of black precipitates
containing almost all of the heavy metal (Au, Bi)
introduced into the reaction mixture.
It should be noted that analogous reactions with
SbPh3 are known to give a stable 1:4 complex, [Au(Sb-
Ph3)4]+X-.9,11 The corresponding bismuth compounds
have never been observed in any of the above experi-
ments.
The arylation products generated from (thioether)gold
chlorides are all inherently unstable because of the poor
ligand properties of the R2S donor molecules. In con-
trast, (phosphine)gold alkyls and aryls are known to be
stable compounds.7 In subsequent experiments, there-
fore, (R3P)AuCl complexes were also employed as re-
agents for R3Bi substrates. The reaction of (Ph3P)AuCl
with BiPh2Me in dichloromethane at -78 °C was found
to be very slow, while upon warming to room temper-
ature it led to decomposition. Only small amounts of
(Ph3P)AuPh were detected in the reaction mixture by
NMR spectroscopy.
To enhance the reactivity of the gold complex, the
chloride was converted into the tetrafluoroborate by
metathesis with AgBF4 to produce [(Ph3P)Au]+BF4- (in
dichloromethane at -78 °C). These solutions reacted
rapidly with BiMe3, BiPh2Me, and BiPh3, but only the
bismuthines containing phenyl groups gave a stable
arylation product, which was identified as {C6H5[Au(P-
Ph3)]2}+BF4- by NMR spectroscopy and mass spectrom-
etry. From the reaction mixture obtained with BiMe3
only [Au(PPh3)2]BF4 could be isolated as a decomposi-
tion product (Scheme 3).
The reaction of (tht)AuCl with BiPh3 (1:4, 1:2, and
1:1) may serve as an example: at room temperature and
in CD2Cl2 as a solvent, immediate decomposition was
observed, while at -78 °C a yellow color developed
which turned to deep purple with formation of a dark
precipitate upon removal of the solvent. Attempts made
with MePh2Bi gave similar results. If the temperature
did not exceed -50 °C, the dark products could be
1
redissolved in CD2Cl2. These solutions showed H NMR
resonances that could be assigned to (tht)AuPh in both
cases, but the products could not be isolated, owing to
the limited stability.
When (Me2S)AuCl was introduced instead of (tht)-
AuCl and treated with BiPh3, BiPh2Me, or Bi(C6H4OMe-
2)3, the results indicated the formation of thermally
unstable (Me2S)AuPh or (Me2S)Au(C6H4OMe-2), respec-
tively. The above reactions are therefore formulated as
arylation reactions (Scheme 1) which leave the corre-
sponding diarylbismuth chlorides Ar2BiCl as byprod-
ucts.
Sch em e 1
(Me2S)AuCl + Ar2RBi -78 °C8
(Me2S)AuAr + ArRBiCl
The results show that the triorganobismuthines R3-
Bi perform as organylating agents for the strong accep-
tor [(Ph3P)Au]+BF4-, but the primary products of the
type (Ph3P)AuR are aurated further by the excess of the
gold component.14 This leads to decomposition in the
gold methyl case but to a stable product for the gold
phenyl case.
Str u ctu r a l Stu d ies. In the course of the present
investigations two structures have been determined in
order to support the assignments based on analytical
and spectral data for one arylgold and one arylbismuth
compound.
It was only the reaction of (Me2S)AuCl with equimolar
quantities of Bi(C6H4CH2NMe2-2)3 that led to a stable
product, which was identified as [-Au-(C6H4CH2NMe2-
2)-]2. This compound (melting point 119 °C) was
obtained previously using the corresponding lithium
reagent and (triphenylarsine)gold chloride, (Ph3As)-
AuCl,13 but its structure had not been determined. It
appears that in this reaction (Scheme 2) the arylbismuth
compound again acts as an arylating agent (like an
aryllithium compound), but the amino group of the side
chain is then able to substitute the thioether of a
neighboring molecule with ring closure.
Crystals of [Au(C6H4CH2NMe2-2)]2 are monoclinic,
space group P21/c, with Z ) 4 formula units (two dimers)
in the unit cell. The dinuclear molecules were found to
The same product was obtained from the reaction of
tris(2-((dimethylamino)methyl)phenyl)bismuth with (tht)-
AuC6F5 in dichloromethane at -78 °C.
(14) Nesmeyanov, A. N.; Perevalova, E. G.; Grandberg, K. I.;
Lemenovskii, D. A.; Baukova, T. V.; Afanasova, O. B. J . Organomet.
Chem. 1974, 65, 131.
(13) van Koten, G.; Schaap, C. A.; J astrzebski, J . T. B. H.; Noltes,
J . G. J . Organomet. Chem. 1980, 186, 427.

Complexes with a Coordinative Au-Bi Bond
Organometallics, Vol. 22, No. 20, 2003 4081
Sch em e 3
F igu r e 1. Disordered molecular structure of the compound
[Au(C6H4CH2NMe2-2)]2 (ORTEP drawing with 50% prob-
ability ellipsoids, H atoms omitted for clarity; sof 50/50).
Selected bond lengths (Å) and angles (deg): Au1-N1 )
2.152(10), Au1-C11 ) 2.042(15), Au1-N2 ) 2.1371(2),
Au1-C21 ) 2.034(14), Au1‚‚‚Au1A ) 2.9176(5); N1-Au1-
C11 ) 179.7(5), N2-Au1-C21 ) 179.4(4).
F igu r e 2. Molecular structure of the compound Bi(C6H4-
OMe-2)3 (ORTEP drawing with 50% probability ellipsoids;
only one of the two crystallographically independent mol-
ecules is shown). Selected bond lengths (Å) and angles
(deg): Bi1-C111 ) 2.248(7); B1-O11 ) 3.097; C111-Bi-
C11A ) 93.5(2).
be disordered, and the structure was solved using a
model illustrated in Figure 1. The dinuclear units are
based on a ten-membered ring with a transannular Au-
Au contact of 2.9176(5) Å, representing significant
aurophilic bonding. The compound is a rare case where
linearly two-coordinate gold has an aryl group trans to
an amine ligand. This situation is generally not expected
to be very stable, but obviously the support by the ring
structure and by the transannular metal-metal inter-
action leads to a more robust configuration.
der Waals radii (>3.60 Å),17 suggesting weak Bi-O
donor/acceptor interactions of the metal center with the
methoxy groups.
Con clu sion s
All attempts to prepare gold(I) bismuthine compounds
with a Au-Bi coordinative bond were unsuccessful.
Reactions of a series of complexes of the type L-Au-X
(with L ) thioether, phosphine ligands and with X )
Cl, BF4, C6F5 anions) with trialkyl, triaryl, or mixed
alkyl/aryl bismuthines gave organogold complexes which
are the products of transmetalation processes. Bismuth-
ines thus act as organometallic reagents for gold in all
cases. The products with thioether ligands R-Au(SR2)
were found to be unstable above -50 °C; those with
phosphine ligands R-Au(PR3) could be detected in
solution by NMR spectroscopy but were not separated
from the diorganobismuthine compounds R2BiX. The
primary phenylation product PhAu(PPh3) was aurated
Crystals of Bi(C6H4OMe-2)3 are rhombohedral, space
group R3h, with Z ) 24 molecules in the unit cell. The
bismuth atom of one of the two independent molecules
resides on a 3-fold axis which relates the three aryl
substituents in what can be described as a propeller
conformation (Figure 2). The second molecule has no
crystallographically imposed symmetry and is disor-
dered. Superpositions show that the differences in the
molecular structures are not great and that both right-
and left-handed propellers are present in the unit cell.
The C-Bi-C angles are found in the narrow range
between 92.6(3) and 95.4(3)° and the Bi-C distances
between 2.248(7) and 2.269(9) Å. These parameters are
in good agreement with published data.15 The atomic
distances between the oxygen and bismuth atoms
(3.079-3.118 Å) are longer than standard covalent
Bi-O bond lengths (2.08-2.80 Å)16 but considerably
shortened as compared with the sum of estimated van
further with [(Ph3P)Au]BF4 to give the known phenyl-
- 14
bridged dinuclear complex {C6H5[Au(PPh3)]2}+BF4
.
It was only with the tris(2-((dimethylamino)methyl)-
(16) Wells, A. F. Structural Inorganic Chemistry; Clarendon Press:
Oxford, U.K., 1987.
(15) Suzuki, H.; Matano, Y. Organobismuth Chemistry; Elsevier:
Amsterdam, 2001.
(17) Ogawa, T.; Ikegami, T.; Hikasa, T.; Ono, N.; Suzuki, H. J . Chem.
Soc., Perkin Trans. 1 1994, 3479.

4082 Organometallics, Vol. 22, No. 20, 2003
Schuster et al.
Ta ble 1. Cr ysta l Da ta a n d Da ta Collection a n d
Str u ctu r e Refin em en t Deta ils
phenyl)bismuthine that a stable arylgold complex could
be isolated. Its crystal and molecular structure has been
determined. The 10-membered dimetallacycle features
short transannular aurophilic contacts.
[Au(C6H4CH2NMe2-2)]2
Bi(C6H4OMe-2)3
Crystal Data
C9H12AuN
331.16
monoclinic
P21/c
11.5252(3)
7.7649(2)
11.3199(2)
90
119.416(1)
90
formula
Mr
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Fcalcd (gcm-3
Z
C21H21BiO3
530.36
rhombohedral
R3h
23.160(3)
23.160(3)
25.418(5)
90
90
120
11807(3)
1.790
24
In summary, it appears that tertiary bismuthines
cannot be employed as donor ligands for gold(I) com-
plexes, because the reaction intermediates are subject
to rapid trans-organylation processes to give organogold
complexes. The bismuthines thus react like standard
organometallic reagents such as organolithium, orga-
nozinc, and Grignard reagents. The organogold com-
pounds produced are either thermally unstable (e.g.
with sulfur donors) or stable (as with phosphine donors)
but are difficult to separate from the organobismuth
byproducts. A robust product has only been successfully
isolated in a case where head-to-tail dimerization in a
ten-membered dimetallacyclic system with transannu-
lar aurophilic bonding can lend sufficient stability to the
arylgold complex: [-Au-C6H4CH2NMe2-]2. This com-
pound had been prepared previously via a standard
organometallic route and the correct structure pre-
dicted.13 It is surprising that in this example even a
nitrogen donor is sufficient to afford a stable substitu-
ent/ligand combination.
882.4(1)
2.493
4
)
F(000)
608
166.04
6096
89.75
µ(Mo KR) (cm-1
)
Data Collection
-130
T (°C)
no. of measd rflns
no. of unique rflns
-130
23 915
114 079
1949 (Rint
0.045)
)
5791 (Rint )
0.073)
abs cor
min/Tmax
DELABS23
0.452/0.820
DELABS23
0.692/0.912
T
Refinement
172
no. of refined params
358
final R values
(I >2σ(I))
R1
0.0279
0.0754
0.0487
0.0953
wR2a
Exp er im en ta l Section
a/b
0.000/6.76
0.000/280.60
1.903/-1.243
F
fin(max/min) (e Å-3
)
Gen er a l P r oced u r e. All organometallic syntheses were
performed under a dry deoxygenated dinitrogen atmosphere
using standard Schlenk techniques. All solvents were distilled
from an appropriate drying agent and stored over molecular
sieves (4 Å) and under nitrogen. Solutions were handled at
-78 °C unless otherwise stated and protected against light.
All standard chemicals and Bi(C6H4-OMe-2)3 were pur-
chased from Aldrich or Fluka and used without further
purification. (tht)AuCl,18 (Me2S)AuCl,18 (tht)AuC6F5,18 (Ph3P)-
wR2) {[∑w(Fo2-Fc2)2]/∑[w(Fo2)2]}1/2; w ) 1/[σ2(Fo2)+(ap)2+bp];
a
p ) (Fo2+ 2Fc2)/3.
mL) was added with stirring, at -78 °C, BiPh2Me (37.8 mg,
0.1 mmol). Stirring of the resulting yellow solution was
continued for 5 h at this temperature. The thermolabile
product (Me2S)AuPh contained in the reaction mixture was
1
identified by its 1H NMR resonances. H NMR (CD2Cl2, -60
°C): δ 2.34 (s, 6H, SCH3), 7.1-7.7 (m, 5H, C6H5). The products
decomposed upon warming of the solution above -50 °C with
deposition of dark precipitates.
(Dim eth yl su lfid e)(2-m eth oxyp h en yl)gold (I), (Me2S)-
Au C6H4-OMe-2. The reaction was carried out as described
above, using (Me2S)AuCl (29.5 mg, 0.1 mmol) and Bi(C6H4-
OMe-2)3 (62.5 mg, 0.1 mmol), to yield thermolabile (Me2S)Au-
AuCl,19 Me3Bi,20 MePh2Bi,21 and Bi(C6H4CH2NMe2-2)3 were
22
prepared as described in the literature.
Mass spectra were recorded on a Finnigan MAT 90 spec-
trometer using FAB as an ionization method. NMR spectra
were obtained at various temperatures on J EOL-400 or J EOL-
270 spectrometers. Chemical shifts are reported in δ values
relative to the residual solvent resonances converted to TMS
(1H). 31P{1H} NMR spectra are referenced to external aqueous
H3PO4 (85%). The single-crystal X-ray diffraction measure-
ments were performed at -130 °C on a Nonius DIP 2020
diffractometer using graphite-monochromated Mo KR radia-
tion.
P h en yl(tetr a h yd r oth iop h en e)gold (I), (th t)Au P h . To a
stirred suspension of (tht)AuCl (158 mg, 0.5 mmol) in CH2Cl2
(5 mL) was added, at -78 °C, BiPh3 (220 mg, 0.5 mmol). The
resulting yellow solution was stirred for 5 h at this tempera-
ture. Removal of the solvent (-78 °C!) yielded an extremely
thermolabile deep purple solid containing (tht)AuPh and
byproducts. 1H NMR (CD2Cl2, -60 °C): δ 1.9-2.2 (br s, 4H,
SCH2CH2), 3.0-3.4 (br s, 4H, SCH2CH2), 7.1-7.9 (m, 5H,
C6H5). Introducing 2 or 4 equiv of BiPh3 or BiPh2Me afforded
product mixtures, the NMR spectra of which also contained
this set of resonances. Decomposition started upon warming
above -50 °C with deposition of purple-black precipitates.
(Dim eth yl su lfid e)p h en ylgold (I), (Me2S)Au P h . To a
suspension of (Me2S)AuCl (29.5 mg, 0.1 mmol) in CD2Cl2 (1
1
C6H4OMe-2 and byproducts. H NMR (CD2Cl2, -60 °C): 2.57
(s, 6H, SCH3), 3.69 (s, 3H, OCH3), 6.7-7.5 (m, 4H, C6H4).
Bis(µ-C,N-2-((d im et h yla m in o)m et h yl)p h en yl)d igold -
(I), [-Au -(C6H4CH2NMe2-2)-]2. To a suspension of (Me2S)-
AuCl (29.5 mg, 0.1 mmol) in CD2Cl2 (1 mL) was added with
stirring, at -78 °C, Bi(C6H4CH2NMe2-2)3 (61.2 mg, 0.1 mmol).
The resulting solution was warmed to -30 °C and developed
a pale yellow color as it was stirred for 5 h at this temperature.
Layering the reaction mixture with n-pentane afforded color-
less crystals; mp 119 °C. 1H NMR (CD2Cl2, room tempera-
ture): δ 2.84 (s, 6H, NCH3), 4.08 (s, 2H, CH2), 6.8-7.8 (m,
1
4H, C6H4). H NMR (CD2Cl2, -60 °C): δ 2.66 (s, 3H, NCH3),
2.97 (s, 3H, NCH3), 3.46 (d, 2J HH ) 11.2 Hz, 1H, CH2), 4.62 (d,
2J HH ) 11.2 Hz, 1H, CH2), 6.8-7.8 (m, 4H, C6H4). The
analogous procedure with (tht)AuC6F5 as a precursor also
yields [-Au-(C6H4CH2NMe2-2)-]2.
(µ-C1,C1-P h en yl)bis[(tr ip h en ylp h osp h in e)gold (I)] Tet-
r a flu or obor a te, {C6H5[Au (P P h 3)]2}+BF 4-. A solution of
[(Ph3P)Au]+BF4- was prepared from (Ph3P)AuCl (99.0 mg, 0.2
mmol) and AgBF4 (42.6 mg, 0.22 mol) in CD2Cl2 (3 mL) at -78
°C. After filtration from the silver salts, the cold solution was
added to triphenylbismuthine (88.1 mg, 0.2 mmol). After 4 h
of stirring at this temperature and upon addition of n-pentane,
a thermostable white precipitate was formed, which was
collected, washed with toluene, and dried (127 mg, 48% yield).
1H NMR (CD2Cl2, -60 °C): δ 7.2-7.8 (m, AuC6H5 and m,
PC6H5). 31P {1H} NMR (CD2Cl2, -60 °C): δ 36.3 (s, AuPPh3).
(18) Uso´n, R.; Laguna, A.; Vicente, J . J . Organomet. Chem. 1977,
131, 471.
(19) Baenzinger, N. C.; Bennett, W. E.; Soboroff, D. M. Acta
Crystallogr., Sect. B: Struct. Sci. 1976, 32, 962.
(20) Mlynek, P. D.; Dahl, L. F. Organometallics 1997, 16, 1655.
(21) Kauffmann, T.; Steinseifer, F. Chem. Ber. 1985, 118, 1031.
(22) Kamepalli, S.; Carmalt, C. J .; Culp, R. D.; Cowley, A. H.; J ones,
R. A.; Norman, N. C. Inorg. Chem. 1996, 35, 6179.

Complexes with a Coordinative Au-Bi Bond
Organometallics, Vol. 22, No. 20, 2003 4083
MS (FAB): m/z 995 (70%) [M]+, 722 (98%) [(Ph3P)2Au]+, 459
(100%) [(Ph3P)Au]+, 262 (7%) [Ph3P]+. Introducing BiPh2Me
into the same procedure afforded a product which gave similar
spectra. The values agree with literature data.14
One of the three OMe groups of this part could not be located
in the Fourier map. Further information on crystal data, data
collection, and structure refinement are summarized in Table
1. Important interatomic distances and angles are shown in
the corresponding figure captions. Complete lists of displace-
ment parameters and tables of interatomic distances and
angles have been deposited with the Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
U.K. The data are available on request on quoting CCDS-
215633, 215634.
Cr yst a l St r u ct u r e Det er m in a t ion s. The crystalline
samples were placed in inert oil, mounted on a glass pin, and
transferred to the cold gas stream of the diffractometer.
Crystal data were collected using a Nonius DIP2020 system
with monochromated Mo KR (λ ) 0.710 73 Å) radiation at
-130 °C. The structures were solved by direct methods
(SHELXS-97) and refined by full-matrix least-squares calcula-
tions on F2 (SHELXL-97).23 Non-hydrogen atoms were refined
with anisotropic displacement parameters. Hydrogen atoms
were placed in idealized positions and refined using a riding
model with fixed isotropic contributions. One of the two
crystallographically independent molecules of Bi(C6H4-OMe-
2)3 was disordered and refined in two split positions (sof 88/
12). All atoms except for the bismuth atom of the part with
the lower occupancy were refined with isotropic contributions.
Ack n ow led gm en t. This work was supported by the
Deutsche Forschungsgemeinschaft, the Fonds der Chem-
ischen Industrie, the Volkswagenstiftung, and Heraeus
GmbH.
Su p p or tin g In for m a tion Ava ila ble: Tables giving de-
tails of crystal data, data collection, and structure refinement,
atomic coordinates, isotropic and anisotropic thermal param-
eters, and all bond lengths and angles. This material is
available free of charge via the Internet at http://pubs.acs.org.
(23) Sheldrick, G. M. SHELXL-97: Program for Crystal Structure
Refinement; University of Go¨ttingen, Go¨ttingen, Germany, 1997.
(24) Spek, A. L. Acta Crystallogr., Sect. A 1990, 46, C-34.
OM030464G